Treatment of fibres

ABSTRACT

CELLULOSIC TEXTILES ARE TREATED WITH AN ESTER WHICH CONTAINS, ON AVERAGE, AT LEAST TWO MERCAPTAN GROUPS PER MOLECULE, AND WITH AN AMINOPLAST WHICH IS FREE FROM ETHYLENIC UNSATURATION, AND THE AMINOPLAST IS CURED. THE TREATED TEXTILES HAVE ENHANCED DIMENSIONAL STABILITY, RESISTANCE OF CREASING, AND MAY HAVE PERMANENT CREASES IMPARTED, WHILST HAVING A FULLER, SOFTER HANDLE AND INCREASED TEAR STRENGTH COMPARED TO CELLULOSIC TEXTILES TREATED WITH THE AMINOPLAST ALONE. TYPICALLY, THE ESTER IS PREPARED BY THE REACTION OF (A) A COMPOUND CONTAINING AT LEAST TWO CARBOXYLIC ACID GROUPS, (B) A COMPOUND CONTAINING AT LEAST TWO ALCOHOLIC HYDROXYL GROUPS AND, OPTIONALLY, (C) A COMPOUND CONTAINING NOT MORE THAN ONE CARBOXYLIC ACID GROUP OR ALCOHOLIC HYDROXYL GROUP, ESPECIALLY A MONOMERCAPTOMONOCARBOXYLIC ACID OR A MONOMERCAPTOMONOHYDRIC ALCOHOL.

3,832,131 TREATMENT OF FIBRES Derek James Rowland Massy, and KennethWinter-bottom, Cambridge, England, assignors to Ciba-Geigy AG, Basel,Switzerland No Drawing. Filed Mar. 15, 1972, Ser. No. 235,036 Claimspriority, application Great Britain, Apr. 19, 1971, 9,767/71 Int. Cl.D06m 15/54, 15/36 US. Cl. 8115.6 8 Claims ABSTRACT OF THE DISCLOSURE (a)a compound containing at least two carboxylic acid groups,

(b) a compound containing at least two alcoholic hydroxyl groups and,optionally,

(c) a compound containing not more than one carboxylic acid group oralcoholic hydroxyl group, especially a monomercaptomonocarboxylic acidor a monomercaptomonohydric alcohol.

This invention relates to a process for modifying cellulosic materialsin fibrous form, and to materials so treated.

It is Well known to treat cellulosic materials with aminoplasts.Cellulosic textiles are often treated with these substances to impartdimensional stability, resistance to creasing, or permanent mechanicaleffects such as seersucker effects and pleats. One drawback is that thetear-strength of the treated textile is often lowered, another is thatthe treated textile is often harsher to the touch. These drawbacks have,to a certain extent, been overcome by incorporating softening agentssuch as polyethylene emulsions or adducts of ethylene oxide with phenolsor amines, but for many purposes these agents are insufficientlyeflfective, and give rise to an impairment of the water-absorptionproperties of the treated textile.

It has now been found that, by the use of specified esters containingmercaptan (-SH) groups in conjunction with certain aminoplasts,cellulosic materials having improved properties, in particular textileshaving a fuller, softer handle, can be obtained. Textiles treated inthis manner have, at most, only a slight impairment of theirwater-absorption properties.

Accordingly, the present invention provides a process for modifyingcellulosic fibres which comprises treating the fibres, in the absence ofketratinous material with, in any desired sequence or simultaneously,

(i) An ester which contains on average at least two mercaptan groups permolecule and is obtainable by the reaction of (a) a compound containingat least two carboxylic acid groups,

(b) a compound containing at least two alcoholic hydroxyl groups, andoptionally,

(c) a compound containing not more than one carboxylic acid group oralcoholic hydroxyl group,

at least one of (a), (b), and (c) if used, having one or more mercaptangroups, and

United States Patent Patented Aug. 27, 1974 (ii) An aminoplast which isfree from ethylenic unsaturation, and curing the aminoplast on thefibres.

It is believed, although the usefulness of the invention does not dependon the truth of this belief, that the mercaptain-containing esters whichare employed also undergo curing on the fibres.

The present invention further provides cellulosic fibrous materialsbearing thereon an ester and an aminoplast as aforesaid in the cured orstill curable, state.

As already indicated, treatment of the fibres with the aminoplast andthe ester can take place in any desired sequence. For example, thefibres may be impregnated with a mixture of the aminoplast and theester, and then the aminoplast is cured. Or the fibres may beimpregnated first with the ester and then with the aminoplast, or viceversa, and then the aminoplast is cured. Or the fibres are firstimpregnated with the aminoplast which is then cured, and the fibres aresubsequently treated with the ester.

Cellulosic fibres which may be subjected to the process of thisinvention include cotton, regenerated cellulose (including viscose andcuprammonium rayons), jute, linen, hemp, ramie, sisal, and paper. Theterm cellulosic fibres" includes fibres comprised of a substance derivedfrom a cellulose in which some, but not all, of the three availablehydroxyl groups per anhydrogluco unit have been chemically modified,e.g., by acylation, etherification, or cyanoethylation. Thusmethylcellulose and cellulose monoacetate are included but not, forexample, cellulose triacetate. The cellulosic materials are preferablytextiles, including yarns, threads, woven, nonwoven and knitted fabrics,and garments.

Mixtures of two or more cellulosic fibrous materials, or blends withsynthetic fibres, may also be treated but it should be understood thatblends with keratinous fibres are not included within the scope of thepresent invention.

Preferred esters for use in the process according to this invention arethose estters containing on average not more than six mercaptan groupsper molecule, and they usually have an average molecular weight ofbetween 400 and 10,000 but, if desired, esters having an averagemolecular weight of up to 20,000 or even 40,000 may be used.

Such esters may be those obtainable by the reaction, in any desiredsequence, of

(d) a monomercaptomonocarboxylic acid ora monomercaptomonohydricalcohol,

(e) a compound containing two, but not more than two,

alcoholic hydroxyl groups, and

(f) a compound containing at least three carboxylic acid groups.

If desired, components (e) and (f) may be caused to react to form ahydroxyl or carboxyl-terminated ester which is then esterified with (d).

Such esters may also be those obtainable by the esterification of (g) amonomercaptodicarboxylic acid with,

(h) a compound containing at least two but not more than six alcoholichydroxyl groups and, optionally,

(i) a dicarboxylic acid containing no mercaptan group, or

an anhydride of such an acid, or

(j) a monocarboxylic acid, preferably a monomercaptomonocarboxylic acid,or

(k) a monohydric alcohol, preferably a monomercaptomonohydric alcohol.

Similarly, there may be employed esters obtainable by the reaction, inany desired sequence, of (d) a monomercaptomonocarboxylic acid, or amonomercaptomonohydric alcohol,

(1) a compound containing'at least three alcoholic hydroxyl groups permolecule, and

(m) a compound containing two, but not more than two carboxylicacidgroups per molecule.

3 As those skilled in the art of makingpolyesters will appreciate, acarboxylic anhydride may be used in place of the correspondingcarboxylic acid while a 1,2-epoxide may be substituted for an alcohol,one epoxide group corresponding to two alcoholic hydroxyl groups.

The esters are prepared in a known manner, preferably by heating thereactants together in the presence of a catalyst such as a strong acid(especially an anion exchange resin, toluene-p-sulphonic acid, or 50%sulphuric acid) and of an inert solvent, such as toluene, xylene,trichloroethylene, or perchloroethylene, with which water formed in thereaction can be removed as an azeotrope.

Substances containing at least two carboxylic acid groups, or anhydridesthereof, which may be used as compound (a) include succinic, adipic,phthalic, hexahydrophthalic, sebacic, malic, citric, tricarballylic,pyromellitic and dimerised or trimerised fatty acids, and theiranhydrides (where existing), and thiomalic acid,

HO OCCH CH (SH) COOH otherwise known as mercaptosuccinic acid.

Monomercaptomonocarboxylic acids used as component (d) are usually offormula HOOC-RSH, where 1 to as high as 18 or even 24. There may thus beused mercaptoundecylic acid, mercaptostearic acid, and especiallythioglycollic acid and 2- and 3-mercaptopropionic acid, i.e. r in theabove formula is 1 or 2. Mercaptancontaining aromatic acids may also beused, such as and p-mercaptobenzoic acids.

Monomercaptomonohydric alcohols used as component (cl) commonly have thegeneral formula HORSH, where R denotes a divalent organic radical, theHO group and the SH group being directly bound to carbon atoms of theradical R. Preferably they are also of formula HOC H -SH, where t is apositive integer of from 2 to 18 and especially preferred are those ofthe foregoing formula where r is 2 or 3, such as Z-mercaptoethanol,1-mercaptopropan-2-ol, and Z-mercaptopropan-l- 01, but substances suchas l-chloro-3rnercaptopropan-Z- 01 may also be used.

Compounds containing at least three carboxylic acid groups, oranhydrides thereof, which may be used as component (f) include citricacid, tricarballylic acid, pyromellitic acid, and trimerised linoleicacid, and their anhydrides (where existing).

The monomercaptodicarboxylic acid (g) is usually of formula HOOCRCOOH,

sorbitol, and adducts of ethylene oxide'or propylene oxide with suchalcohols, including mixed polyhydric polyethers obtained by treating aninitiator containing active hydrogen, such as ethylene glycol, with say,propylene oxide, and then tipping the adduct with a second alkyleneoxide, say, ethylene oxide.

Mono'l,2-epoxides which may be used in place of a dihydric alcoholinclude: ethylene oxide, propylene oxide, butylene oxide,1,1-dirnethylethylene oxide, epichlorohydrin, glycidyl ethers ofalcohols (such as n-butyl and isooctyl glycidyl ethers) or of phenols(such as phenyl and p-tolyl glycidyl ethers), N-glycidyl compounds (suchas N-glycidyl-N-methylaniline or N-glycidyl-n-butylamine), and glycidylesters of carboxylic acids (such as glycidyl acetate).

In place of trihydric and higher alcohols there may be usedmonoepoxymonohydric alcohols such as glycidol, or a diepoxide such as adiglycidyl ether of an alcohol or a phenol.

The dicarboxylic acids containing no mercaptan group (i) which may beused are generally of the formula HOOC-R COOH, where R represents adivalent aliphatic, aromatic, or alicyclic residue, and includesuccinic, adipic, phthalic, hexahydrophthalic, sebacic, and malic acids,and dimerised fatty acids or their anhydrides. Although they can beused, ethylenically-unsaturated dicarboxylic acids are not preferred.

The dicarboxylic acids (m) and their anhydrides may be selected fromthose listed above for (i) and also the mercaptan-containingdicarboxylic acids (g) and their anhydrides.

It is often desirable, when preparing a polymercaptan ester for use inthe present invention, to incorporate a monofunctional compound such asa monocarboxylic acid (j) or a monohydric alcohol (k) as achain-terminator. Examples of these are aliphatic alcohols such asmethanol, ethanol, Z-ethylhexanol, Z-methoxyethanol, and monomethylethers of poly(oxyethylene) glycols and poly(oxypropylene) glycols;cycloaliphatic alcohols such as cyclohexanol; aliphatic carboxylic acidssuch as acetic acid, Z-ethylhexanoic acid, stearic acid, and oleic acid;and aromatic acids such as benzoic acid. As already indicated, it isespecially advantageous to use as the chainterminator a compound whichcontains a mercaptan group, examples being monomercaptomonocarboxylicacids and monomercaptomonohydric alcohols and, more specifically,thioglycollic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid,2-mercaptoethanol, and Z-mercaptopropan-l-ol.

The polymercaptan esters are, in general, known substances (see US.Patent Specifications Nos. 2,456,314, 2,461,920, 2,914,585 and3,138,573, French Patent Specification No. 1,503,633 and British PatentSpecification No. 941,829).

The preferred polymercaptan esters used in the process of the presentinvention contain, directly attached to carbon atoms, on average 11groups of formula where a and b are each zero or 1 but are not the same,n is an integer of at least 1 and at most 6, Y and Z each represent adivalent organic radical, and X represents a divalent organic radicalwhich must contain an SH group when n is 1. More specifically, theaverage structures of the preferred esters can be represented by one ofthe formulae and especially by one of the formulae L (XI) D (XIII) (XIV)SH (XVI) R denotes the residue of an aliphatic, cycloaliphatic, oraromatic dicarboxylic acid after removal of the COOH groups,

R denotes the residue of an aliphatic, araliphatie, or cycloaliphaticdiol after removal of the two hydroxyl p R denotes an organic radicalcontaining at least two carbon atoms and directly linked through carbonatoms thereof to the indicated mercaptan-terminated ester chains,

R denotes the residue of an aliphatic, eycloaliphatic, or aromaticdicarboxylic acid containing a mercaptan group, after removal of theCOOH groups,

m is an integer of at least 1,

p is an integer of at least 2, and

R, R, r, and t have the meanings previously assigned.

It will be understood that formulae II to XVII represent the averagestructure of the esters. Because of incomplete esterification, othersubstances may also be present. Further, as already indicated, not allunits designated R, R and R to R need be the same.

Many of these esters are insoluble in water but can be applied asaqueous dispersions or emulsions. They may also be applied from organicsolvents, for example, lower alkanols (such as ethyl alcohol), lowerketones (such as ethyl methyl ketone), benzene, and halogenatedhydrocarbon solvents, especially chlorinated and/ or fiuorinatedhydrocarbons containing not more than three carbon atoms, such as thedry cleaning solvents, carbon tetrachloride, trichloroethylene, andperchloroethylene.

The amount of the ester to be used depends on the effect desired. Formost purposes, a pick-up of from 0.1 to 5% by weight based on thematerial to be treated is suitable. Usually, woven fabrics require from0.2 to 3% by weight of the ester but rather smaller quantities areneeded on knitted fabrics, say from 0.1 up to 1.5% by weight. The handleof the treated material will, of course, depend on the amount of esteremployed, and by simple experiment the least amount required to give thedesired effect may readily be determined. Further, the composition andthe construction of fabrics composed of the fibres also influence theamount of ester required.

The preferred aminoplasts contain, per molecule, at least two groups, offormula CH OR directly attached to an amidic nitrogen atom or atoms,where R denotes a hydrogen atom, an alkyl group of from one to fourcarbon atoms, or an acetyl group. Examples of such aminoplasts are theN-hydroxymethyl, N-al-koxymethyl, and N- acetoxymethyl derivatives ofthe following amides and amide-like substances.

(I) Urea, thiourea, and the cyclic ureas having the formula in which Qdenotes oxygen or sulphur, and Y denotes either a group of formula or adivalent group containting from 2 to- 4 carbon atoms in the chain, whichmay be substituted by methyl, methoxy, and hydroxy groups, and which maybe interrupted by '00-, -o-, or 1 lIR where R denotes an alkyl orhydroxyalkyl group containing up to 4 carbon atoms.

Examples of such cyclic ureas are ethyleneurea (imidazolidin-Z-one),dihydroxyethyleneurea (4,5 dihydroxyimidazolidin-Z-one), hydantoin, uron(tetrahydro-oxadiazin-4-one), 1,2-propyleneurea (4-methylimidazolidin-2-one), 1,3-propyleneurea (hexahydro-2H-pyrimid-2-one),hydroxypropyleneurea (5hydroxyhexahydro-ZH-pyrimid- 2-one),dimethylpropyleneurea (5,5-dimethylhexahydro- 2H-pyrimidone),dimethylhydroxypropyleneurea and dirnethylmethoxypropyleneurea(4-hydroxyand 4'me thoxy-S,5-dimethylhexahydro2H-pyrimid 2 one), 5-ethyltriazin-Z-one and 5-(2-hydroxyethyl)triazin-Z-one.

(II) Carbamates and diearbamates of aliphatic monohydrie and dihydriealcohols containing up to four carbon atoms, e.g. methyl, ethyl,isopropyl, 2-hydroxyethyl, 2-methoxyethyl, 2-hydroxy-n-propyl, and3-hydroxy-npropyl carbamates, and ethylene and 1,4-butylenedicarbamates.

(III) Melamine, and other p-olyamino-l,3,5-triazines.

If desired, aminoplasts containing both N-hydroxymethyl andN-alkoxymethyl, or N-hydroxymethyl and N- acetoxymethyl groups, may beused (for example, a hexamethylol melamine in which from 1 to 5 of themethylol groups have been so etherified or esterified) The aminoplast isusually applied as such but when a urea-formaldehyde ormelamine-formaldehyde product is to be used, it may, if desired, beformed in situ in a conventional manner from a urea-formaldehydeconcentrate or melamine-formaldehyde concentrate and the requisiteadditional urea or melamine.

The aminoplasts employed are, in general, soluble in water and may beapplied from aqueous solution; or they may be applied from aqueousemulsions, from solutions in the dry-cleaning solvents, or fromsolutions in mixtures of water and a suitable co-solvent, such asmethanol.

The proportions of the ester and the aminoplast can vary widely; theremay be employed, per thiol group equivalent of the ester, from 2 to 50or even 75, but usually from 5 to 40, N-methylol, N-alkoxymethyl or N-acetoxymethyl group equivalents of the aminoplast.

The desired effects may not be fully obtainable until substantially allthe ester has cured. At room temperatures (say, 20 C.) this may takefrom five to ten days or even longer. When the ester has been appliedbefore, or with, the aminoplast, and heat is used to promote curing ofthe aminoplast, the ester cures rapidly. The curing reaction can also beaccelerated greatly by the use of a catalyst and generally it ispreferred to add the catalyst to the material to be treated at the sametime as the ester is applied, although it may be added before orafterwards if desired. The curing time can be controlled by selecting anappropriate catalyst and the choice of curing time will depend on theparticular application of the process according to the invention. Thecatalysts may be bases, siccatives, oxidative curing agents, sulphur,sulphur-containing organic compounds, salts and chelates of heavymetals, and free-radical catalysts such as azodiisobutyronitrile,peroxides and hydroperoxides, or combination of these. As organic basesthere may be used primary or secondary amines such as the loweralkanolamines, e.g., monoand di-ethanolamine, and polyamines, e.g.,ethylenediamine, diethylenetriamine, triethylenetetramine,tetraethylenepentamine, and hexamethylenediamine. As inorganic basesthere may be used the water-soluble oxides and hydroxides, e.g., sodiumhydroxide, water-soluble strongly basic salts such as trisodiumphosphate, and also ammonia. As sulphur-containing organic compoundsthere may be used compounds in which the sulphur atoms are notexclusively present as mercaptan groups and which aremercaptobenzothiazoles and their derivatives, dithiocarbamates, thiuramsulphides, thioureas, disulphides, alkyl xanthogen sulphides and alkylxanthates. Examples of siccatives are calcium, copper, iron, lead,cerium, and cobalt naphthenates. Examples of suitable peroxides andhydroperoxides are cumene hydroperoxide, tert. butyl hydroperoxide,dicumyl peroxide, dilauryl peroxide, methyl ethyl ketone peroxide,di-isopropyl peroxydicarbonate, and chlorobenzoyl peroxide.

Yet other catalysts are salts of a heavy metal with an acid having anacid strength (-log pK) below 5, or chelates of a heavy metal, includingchelates which are also salts. By heavy metal is meant one classified asheavy in Langes Handbook of Chemistry, revised th Edition, McGraw-HillBook Co., at pp. 6061, that is, a metal of group IB, IIB, IIIB, IVB, VB,VIB, VIIB, or VIII, a metal of group IIIA having an atomic number of atleast 13, a metal of group IVA having an atomic number of at least 32,or a metal of group VA having an atomic number of at least .51.Preferably the metal is a member of group IB, IIB, IVB, VB, VIB, VIIB,or VIII, particularly the first series of such metals, i.e., titanium,vanadium, chromium, manganese, nickel, and especially iron, cobalt, andcopper. Suitable salt-forming, non-drying acids are mineral acids,especially hydrochloric, hydrobromic, nitric, sulphuric, phosphorous,and phosphoric acids, and organic acids such as chloracetic, fumaric,maleic, oxalic, salicylic and, more especially, citric acid. Suitablechelating agents include those in which the chelating atoms are oxygenand/or nitrogen, for example, 1,2- and 1,3-diketones such asacetylacetone, alkylenediamines such as ethylenediamine and, moreparticularly, ethylenediaminetetra-acetic acid.

The amount of catalyst used can vary widely. In general from 0.1 to 20%,and preferably from 1 to 10%, by weight based on the weight of the esterused is required, although much larger quantities can be used.

Curing of the ester is also assisted by using elevated temperatures andif especially rapid results are required then temperatures in the range30 to 180 C. may be used. High humidities also tend to accelerate curingin the presence of catalysts.

The aminoplast may be cured at room temperature, or as alreadyindicated, at elevated temperatures. The mechanism by which the esterexerts its effect in conjunction with the aminoplast is not known. It isbelieved that either the -SH groups of the ester react with theN-methylol groups (present as such or formed in situ from esterified oretherified N-methylol groups), or oxidation of the -SH groups occur,molecules of the ester being coupled by means of disulphide bridges. Theutility of this invention, however, does not depend on the truth of thisbelief.

In many cases it is desirable to include a catalyst for curing theaminoplast. Catalysts which may be used include latent acid compounds(which may be metal salts), or mixtures thereof, or certain basicsubstances. Ammonium salts which are latent acids, developing acidity inthe mixture on heating, include ammonium chloride, ammonium dihydrogenphosphate, ammonium sulphate, and ammonium thiocyanate. These ammoniumsalts may be used admixed with metal salts which have a similarcatalytic effect. Amine salts may also be used, e.g., Z-amino-Z-methylpropanol hydrochloride. Among suitable latent acid metal saltsare zinc nitrate, zinc fiuoroborate, zinc chloride, zirconiumoxychloride, magnesium chloride, magnesium fiuoroborate, and magnesiumdihydrogen orthophosphate. These catalysts are generally used atconcentrations of 0.3% to 5% by weight, calculated on the weight ofresin-forming materials of the aminoplast. There may also be usedstronger acids, such as hydrochloric and sulphuric acids, which may beused as aqueous solutions (say, as 4- to 8-normal solutions) or whichmay be dissolved in a mixture of water and a solvent which is immiscibleor partly miscible with water, and also acidic gases. Basic substanceswhich may be used include sodium bicarbonate and sodium carbonate.

When strong acid catalysts are used, in liquid or gaseous form, heatingmay not be required. In other cases it may be necessary to heat thetreated material, e.g., at a temperature of to 200 C. for 30 seconds to10 minutes, and preferably to 180 C. for 2 to 7 minutes.

To impregnate the fibres it is particularly convenient to use an aqueousemulsion comprising (i) an ester as aforesaid,

(ii) an emulsifying agent which is preferably nonionic or anionic (forexample, compounds containing polyoxyethylene chains),

(iii) a protective colloid (such as sodium carboxymethylcellulose,hydroxyethylcellulose, methoxyethylcellulose, and a methyl vinylether-maleic anhydride copolymer in the form of an alkali metal orammonium salt).

The ester, the aminoplast, and the catalyst if used, can be applied tothe material in conventional Ways. For example, where fabric or yarn isto be treated, they may be padded on, or the material may be immersed ina bath. If garments or garment pieces are to be treated then it isconvenient to spray them on, and more convenient still to tumble thegarments with the solution, emulsion, or suspension.

A crease-resistant finish may be applied to cellulosic textiles byimpregnating with the ester, an aminoplast, and a catalyst for theaminoplast, drying, and curing the fabric in a fiat state at a hightemperature. Compared to that treated with aminoplast only, fabrictreated in the above manner is considerably softer and has eithersubstantially improved dry crease-resistance with no further loss intear strength or substantially improved tear strength with no loss indry crease-recovery.

Alternatively, a celulosic textile fabric having good wetcrease-recovery may be obtained by impregnating the material with anaqueous solution of an aminoplast (such as methylolateddihydroxyethylene urea) and with a strong acid catalyst (e.g.,hydrochloric acid) and maintaining the Wet fabric in a flat state,usually for 16 to 24 hours, rinsing, neutralising and drying the fabric,and then treating it with the ester (usually as an aqueous emulsion, andpreferably containing a catalyst). Material so aftertreated with theester has much better wet crease-recovery than, and tear strength asgood as that of, that treated with the aminoplast alone.

A durably pressed cellulosic garment may be made by treating fabrics inpiece form with the ester (preferably as an aqueous emulsion), anaminoplast, and a catalyst for the aminoplast, and drying theimpregnated fabric, fashioning the sensitised fabric into garments,inserting creases or pleats, and curing the aminoplast, preferably at anelevated temperature. Compared to a garment treated with the aminoplastonly, the garment is much softer to the touch and has a much betterbalance of crease-recovery and strength.

Unlike other softeners currently used, the esters used in the process ofthis invention do not impair the water absorption properties of thetreated cellulosic materials.

The compositions used in the process of this invention may containantisoiling, antistatic, bacteriostatic, rotproofing, fiarneproofing,and wetting agents. They may also contain water-repellents, such asparffin wax, and fluoroescent whitening agents.

The following examples illustrate the invention. Unless otherwisespecified, parts and percentages are by weight. The esters used wereprepared as follows.

Thiol A A mixture of 1,1,1-trimethylolpropane (26.8 g.),polyoxypropylene glycol of average molecular weight 425 (170 g.), adipicacid (58.4 g.), thioglycollic acid (55.2 g.), toluene-p-sulphonic acid(3 g.), and perchloroethylene (350 ml.) was heated under reflux in anatmosphere of nitrogen. Water formed during the reaction (25 ml.) wasremoved as its azeotrope with perchloroethylene. The mixture was cooledand washed with water, the organic layer was separated and the solventwas evaporated oif to leave Thiol A (278.9 g.) having a thiol content of1.88 equiv./ kg.

Other esters listed in Table I were prepared in a similar manner exceptthat, in making Thiol U, the toluene-psulphonic acid was replaced by 1ml. of 50% aqueous sulpuric acid.

TABLE I Components Thiol content (equiv./

Molar Substance ratio Glycerol Adipic acid- Butane-1 ,4-diol.Thioglycollic acid Trimer acid Empol 1043 Pilgygoxypropylene glycol,average mol. wt.

Thioglycollic acid Pggaxypropylene triol, average mol. wt.

Mercaptosuccinic acid n-pentanol Pcltygxypropylene triol, average mol.wt.

Adipic acid Q-mercaptoethanol P il(%%xypropylene glycol, average mol.

Thiol H Butane-1 .4-diol 1. 64

Thioglycollic acid TABLE IContinued Components Molar Thiol Substanceratio {Polyoxypropylene triol average mol. wt. 700. 1 I

Hexane-1,2,6-triol.

J Ptllggoxypropylene glycol, average mol. wt.

Thioglycollic acid Glycerol Adipic acid Polyoxyethylene glycol, averagemol. wt. 400. Thioglycollic acid 1,1,1-trirnethylo1propane Succinic acidComerginol 65. Thioglycollic acid M lrimer acid Empol 1043Butane-1,4-diol 3-mercaptopropionic acid 1,1 ,l-trimethylolpropane-Adipic acid Pillzygoxypropylene glycol, average mol. wt.

3-mer captopropionic acid {1,1,1-trimethylolpropane adipic acid 0 Adipicacid 2,2-bis(p-(2-hydroxypropoxy) phenyDpropane. Thioglycollic acidGlycerol Adipic acid Poilggoxypropylene glycol, average mol. wt.

Thioglycollic acid Polyoxypropylene triol, average mol. wt. 700.

Adipic acid Thioglycollic acid Polyoxyethylene glycol, average mol. wt.300: Thioglycollic acid Pgloylgxypropylene triol, average mol. wt.

Succinic anhydride 48 Z-mercaptoethanol Pentaerythritol-propylene oxidetetrol adduct average mol. wt. 650. "Dimer acid Empol 1022Z-mercaptoethanol lycerol Phthalic anhydride- Butane-1,4-diol.Thioglycollic acid v {P(il(]}6t())xypl0l)l6ll8 glycol average mol. wt.

Mercaptosuccinic acid w {Pgloygxypropylene glycol average mol. wt.

. 0.40 Mercaptosuccinic acid Polyoxypropylene glycol average mol. wt.

Mercaptosuccinic acid Y {Butane-IA-diol Mercaptosuccinic acid Z{Comerginol 65...

Mercaptosuccinic acid. Thioglycollic acid Pilggoxypropylene glycolaverage mol. wt.

Mercaptosuccinic acid Adipic ac" [Acetic acid H H p-n- H reu e:F-INFNDUIOIO Ho Hm clwbhyhifi lh Hose Hutchw man-w: unl t-wretch d:remweeeawwmmrwrorowee term-meow:

"Trimer acid Empol 1043 is available from Unilever-Emery N.V., Gouda,Holland. It is a trimerised unsaturated 0 fatty acid, having an averagemolecular Weight of about 800 and a carboxyl content oi about 3.4equiv./kg. Dimer acid Empol 1022 was obtained from the same source: itis a dimerised unsaturated 0" fatty acid, having an average molecularweight of about 570 and a carboxyl content of about 3.4 equiv.

Comerginol 65 was obtained from Bibby Chemicals Ltd., Liverpool. It hasan average molecular weight of about 700, and a hydros yl value of -165.It consists essentially of diprlmary alcohols, prepared by catalytichydrogenation of the methyl esters of long chain aromatic-aliphaticfatty acids, together with, as by-products, small amounts of monohydricand tr hydric alcohols.

Emulsions of the polythiols were prepared by mixing the followingcomponents at room temperature with a Silverson mixer until a uniformemulsion resulted Emulsifying agent 1 denotes an adduct of a mixture ofCm and C18 aliphatic primary amines (1 mol) and ethylene oxide (70mols).

11 1 Emulsifying agent 1 denotes an adduct of a mixture of C1 and Caliphatic primary amines (1 mol) and ethylene oxide (70 mols).

EXAMPLE 1 Samples of bleached cotton poplin (108 g. per square metre)were padded with a liquor (Liquors l7) so that the uptake was 70%. Thesamples were dried for minutes at 70 C. on tenter frames to theiroriginal dimensions, and then they were cured by heating for 5 minutesat 150 C. The crease angles and tear strength properties of the treatedcloth were measured and are given in Table II.

Liquor 1 Aminoplast A 60 MgCl -6H O 18 per litre of water Liquors 2-7Liquors 2-7 were the same as Liquor 1 but contained 20 g. of ThiolResins A, B, C, D, E, or F respectively, in emulsion form, per litre ofwater.

Aminoplast A is a co-condensate of a methylated hexamethylolmelaminecontaining 4.5 methoxymethyl groups per molecule withN,N'-dimethylolethyleneurea.

In this and the following examples, the dry crease angles of the treatedsamples were measured by the Monsanto method. Twelve specimens (sixfolded warpwise, six folded weftwise) were used in each test and thespecimens were creased under a 2 kg. load for 3 minutes and allowed torecover, suspended over a wire, for 3 minutes before the crease angleswere measured. The values given in the tables are the average of the sixobtained by adding the warpwise value to the corresponding weftwisevalue and dividing by two. Tear strengths were determined by theElrnendorf method according to TAPPI Standard T 414n49. Three samples,each 63 mm. X 63 mm., were used, and the tear strengths were measured inthe warp direction. All measurements of crease angle and tear strengthswere determined on cloth which had been conditioned in an atmosphere of66% relative humidity and a temperature of 25 C. for at least 8 hours.

TAB LE I I Crease Tear angle strength Liquor (deg) 03-) 1 (control) 91336 7 Untreated Inclusion of the thiol did not impair thechlorine-resistant properties of fabric treated with the above liquors.

Similar results could be achieved by using any of Polythiols G to Z andA in place of the Polythiols A to F.

EXAMPLE 2 Example 1 was repeated, using the following liquors.

Liquor 8 Aminoplat B 100 MgCly per litre of water Liquors 9-12 Thesample treated with Liquor 11 had a particularly soft handle.

EXAMPLE 3 Samples of the cotton poplin described in Example 1 werepadded with Liquors .1 or 8 so that the uptake was and dried for 10minutes at 70 C. on tenter frames to their original dimensions, thenthey were heated for 5 minutes at 150 C. to cure the resin. Next, someof the patterns were padded with solutions of a thiol inperchloroethylene so that the uptake of solution was 150% and that ofthiol was 2%. They were dried as before and then allowed to cure bybeing kept at room temperature for 1 day. The crease angles and tearstrengths are shown in Table IV.

Liquor 8 plus Thiol F EXAMPLE 4 Cotton poplin was padded with a solutionof a thiol in perchloroethylene so that the uptake of the solution was150% and that of the thiol was 2%. The samples Were dried for 10 minutesat 70 C. on tenter frames to their original dimensions and then kept atroom temperature for 24 hours. Next, they were treated with eitherLiquor 1 or Liquor 8, dried as above, and finally cured for 5 minutes at150 C. Results obtained are shown in Table V.

TABLE V Crease Tear angle strength Treated with (deg) (g.)

Untreated 43 1, 016 Liquor 1 only. 91 336 Thiol A plus Liquor 1- 106 384Thiol B plus Liquor 1 112 384 Thiol 0 plus Liquor 1 108 368 Thiol D plusLiquor 1. 115 400 Thiol E plus Liquor 1. 112 368 Thiol F plus Liquor 1116 416 Liquor 8 only 98 416 Thiol A plus Liquor 8. 112 352 Thiol B plusLiquor 8 126 384 Thiol 0 plus Liquor 8--.. 116 320 Thiol D plus Liquor 8116 384 Tluol E plus Liquor 8-... 114 384 Thiol F plus Liquor 8 117 352The sample treated with Thiol E and Liquor 1 had a particularly softhandle.

EXAMPLE 5 Samples of a bleached viscose fabric (177 g. per square metre)were padded with a liquor (Liquors 13-19) such that the uptake of liquorwas 80%. The samples were dried at 70 C. for 10 minutes on tenter framesto their original dimensions, then cured by heating for 5 minutes at C.Table VI shows the crease recovery and tear strength properties of thetreated materials.

13 Liquor 13 G. Aminoplast C 200 NH H PO 12 per litre of waterAminoplast C is a 50% aqueous solution of a methylated urea-formaldehyderesin in which the U:F molar ratio is 121.8.

Liquors 14-19 Liquors 14-19 were the same as Liquor 13 but contained inaddition 20 g. of Thiols A-F respectively, in emulsion form.

TABLE VI Crease Tear Treated with angle strengt liquor (deg) (g.)

EXAMPLE 6 Samples of the viscose cloth which was described in Examplewere padded to 80% pick-up with Liquor 13, dried for 10 minutes at 70 C.on tenter frames to their original dimensions, and then heated for 5minutes at 150 C. to cure the aminoplast. Next, some of the patternswere padded with a solution of a thiol in perchloroethylene so thatuptake of the thiol was 2% The samples were dried as before and thenallowed to stand for 24 hours at room temperature before the creaserecovery properties and tear strengths of the treated fabric wereassessed.

Liquor 13 plus Thiol F..'

EXAMPLE 7 The viscose fabric described in Example 5 was treated with asolution of a thiol in perchloroethylene so that the EXAMPLE 8 Samplesof a cotton poplin similar to that described in Example 1 were paddedwith a liquor (Liquors 20-28) so that the uptake was and dried for 10minutes at 60 C. on tenter frames to their original dimensions. Theywere then cured by heating for 5 minutes at C. The crease angles andtear strength properties of the treated cloth were measured. The handleof the treated cloth was assessed by a panel, and the absorption of thematerials was determined by the American Association of Textile Chemistsand Colorists Test Method 39-1952. The results are given in Table IX.The treated materials were washed in a solution of 2 g./l. soap and 0.8g./l. soda ash in an English Electric Reversomatic washing machine seton programme 5, dried for 10 minutes in a Parnall Tumble Drier on a fullheat, and their crease recovery and tear strength properties measured.

Liquor 20 Aminoplast D 120 MgCl -6H O 20 per litre of water Liquors21-26 Liquors 21-26 were the same as Liquor 20 but contained in addition20 g. of Thiol Resin A, B, C, D, E, or F respectively, in emulsion formper litre of water.

Liquors 27 and 28 TABLE IX Crease angle (deg.) Tear strength (g.) Waterabsorption Liquor Unwashed Washed Unwashed Washed Handle (secs) 107 105156 156 Harsh 3.9 111 102 164 156 Fairly soft.--" 4.0 114 103 172 Fairlyharsh--- 4.7 127 117 172 240 Fairly soft 8.7 122 112 220 200 t 6. 2 120107 196 Fairly soft 3.8 121 108 204 180 it 7.0 113 104 208 192 Fairlyhars 7.2 117 99 276 232 t 1,700 42 45 520 364 .--..do 5.2

EXAMPLE 9 per litre of water. The patterns were placed on a roller,covered with a film of polyethylene and held wet for 18 hours whilst theroller was rotated slowly. The patterns were then well rinsed withwater, a solution of 5 -g./l. of sodium carbonate, water again andfinally dried on tenter frames at their original dimensions.

Some of the patterns were then treated with Liquors 29- 33 to 70%expression, dried for 10 minutes at 70 C. and then allowed to cure for 5days at room temperature. The wet and dry crease recovery angles and thetear strength of the treated cottons were measured and are recorded inTable X.

Liquors 29-33 Liquors 29-33 contained g. of Thiol Resin C per litre ofwater; Liquors 30-33 contained in addition 2 g. of monoethanolamine, 2g. of sodium dimethyl dithiocarbamate, 0.1 g. of copper sulphate, or 10g. of 100 vol. hydrogen peroxide per litre of water respectively.

TABLE X Crease angle (deg) Tear strength Liquor Wet Dry (g.)

Aminoplast D only 112 61 272 29 127 70 320 30.. 126 70 312 31 118 68 30832- 136 66 312 33 128 70 328 Untreated 59 48 560 where R denotes theresidue of an acid of 4 to 36 carbon atoms selected from aliphatic,cycloaliphatic, and aromatic dicarboxylic acids after removal of the twocarboxylic groups,

R denotes the residue of a diol of at least 4 carbon atoms selected fromaliphatic, araliphatic, and cycloaliphatic diols after removal of thetwo hydroxyl groups,

R denotes an organic radical containing at least 2 carbon atoms anddirectly linked through carbon atoms thereof to the indicatedmercaptan-terminated ester chains.

R denotes the residue of an acid of three to four carbon atoms selectedfrom aliphatic, dicarboxylic acids containing a mercaptan group, afterremoval of the two carboxyl groups,

In is an integer of at least 1,

p is an integer of at least 2 and no more than 6, and R is a divalenthydrocarbon radical of 1 to 24 carbon atoms. y

2. The process of claim 1, wherein the polyester material is selectedfrom the formulae:

(I), (IV), and (V) Where is C H (II), (III), (IV), and (VIII) Where R isC,H and (VII) and (VIII) where R is -CHTCH;

wherein r is an integer of 1 to 24, t is an integer of 2 to 18, and theaverage molecular weight of the polyester material is 400 to 10,000.

3. Process according to claim 1, in which there is used from 0.1 to 5%by weight of the polyester material, calculated on the weight of thecellulosic fibres treated.

4. Process according to claim 1, in which there is employed from 5 to 40group equivalents of a group selected from the class consisting ofN-methylol, N-alkoxymethyl, and N-acetoxymethyl, per thiol groupequivalent of the polyester material.

5. Process according to claim 1 wherein a catalyst for curing thepolythiol is also applied which is selected from the group consisting ofbases, siccatives, oxidising agents, sulfur, sulfur-containing organiccompounds, free-radical catalysts, salts of a heavy metal with an acidhaving an acid strength (log pK) below 5, and chelates of a heavy metal.

6. Process according to claim 1 wherein a catalyst for curing theaminoplast is also applied which is selected from the group consistingof acids, latent acid compounds, and bases.

7. Process according to claim 1 in which the treated cellulosic fibresare heated at a temperature of from to 200 C. for from 30 seconds to 10minutes to cure the aminoplast.

8. Cellulosic fibrous materials, free from keratinous material, bearingthereon a polyester material and an aminoplast as specified in claim 1.

3,476,697 11/1969 Clements 117-1395 X 3,706,527 12/1972 Dobinson et al8-115.6 X 2,461,920 2/1949 Pratt 260-828 X 3,498,821 3/1970 Hanson8-115.6 X 3,526,474 9/1970 Reeves et al. 8-185 X 3,576,591 4/1971 Cusanoet a1 8-185 3,350,162 10/1967 Beck 8185 X 3,690,942 9/ 1972 Vandermaaset a1. 117139.5 X 3,703,352 11/1972 Dobinson et a1. 117141 X 3,706,52812/1972 Dobinson et a1. 117-128 HERBERT B. GUYNN, Primary Examiner US.Cl. X.R.

UNITED s'rAirrfa FATsN'r OFFICE CER'IIFICATE ()F CORRECTION Patent No. I3, 832,;31 Dated August 27, 1974 Inventor(s) Derek James Rowland Massyet a1 It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Column 16, claim 2, lines 1 4-19, delete the structural formula whichnow reads (I), (IV), and (V') where is -C H (II), (III), (IV), and(VIII) where R is -C H and (VII) and (VIII) where R is -CH -(l3H-;

and substitute the following structural formula I, IV, and V where R is-C H VII and VIII where R is CH2-CH l SH Signed and sealed this 1st dayof July 1975.

(SEAL) Attest:

, C. MARSHALL DANDY RUTH C. MASON Commissioner of Patents attestingOificer and Trademark

